N-Phenylsulfonyl-N&#39;-pyrimidinylureas

ABSTRACT

N-Phenylsulfonyl-N&#39;-pyrimidinyl- and -triazinylureas of the general formula ##STR1## and the salts of these compounds with amines, with alkali or alkaline-earth metal bases or with quaternary ammonium bases, have good pre- and post-emergence selective, herbicidal and growth-regulating properties. 
     The symbols in this formula are as follows: 
     A is a C 3  -C 6  -alkynyl group, 
     E is the methine group or nitrogen, 
     X is oxygen, sulfur or a sulfinyl or sulfonyl bridge, 
     Z is oxygen or sulfur, 
     m is the number one or two, 
     R 1  is hydrogen, halogen, C 1  -C 5  -alkyl or C 2  -C 5  -alkenyl or a group --Y--R 5 , 
     R 2  is hydrogen, halogen, C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or C 1  -C 4  -haloalkyl, or a group --Y--R 5 , --COOR 6 , --NO 2  or --CO--NR 7  --R 8 , 
     R 3  and R 4  independently of one another are each hydrogen, C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, C 1  -C 4  -alkylthio, C 1  -C 4  -haloalkyl, C 1  -C 4  -haloalkoxy, halogen or alkoxyalkyl having at most 4 carbon atoms, 
     R 5  and R 6  are each C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or C 2  -C 6  -alkynyl, 
     R 7  and R 8  independently of one another are each hydrogen, C 1  -C 5  -alkyl, C 2  -C 5  -alkenyl or C 2  -C 6  -alkynyl, and 
     Y is oxygen, sulfur or a sulfinyl or sulfonyl bridge.

This is a division of application Ser. No. 396,959, filed on July 9,1982, now U.S. Pat. No. 4,443,243.

The present invention relates to novel N-phenylsulfonyl-N'-pyrimidinyl-and -triazinylureas which have a herbicidal action and an actionregulating plant growth, to processes for producing them, tocompositions containing them as active ingredients, and also to the usethereof for combating weeds, particularly selectively in cultivatedcrops, or for regulating and reducing plant growth. The inventionrelates in addition to novel phenylsulfonamides andN-phenylsulfonylcarbamates produced as intermediates.

The N-phenylsulfonyl-N'-pyrimidinyl- and -triazinylureas according tothe invention correspond to the general formula I ##STR2## wherein A isa C₃ -C₆ -alkynyl group,

E is the methine group or nitrogen,

X is oxygen, sulfur or a sulfinyl or sulfonyl bridge,

Z is oxygen or sulfur,

m is the number one or two,

R₁ is hydrogen, halogen, C₁ -C₅ -alkyl or C₂ -C₅ -alkenyl or a group--Y--R₅,

R₂ is hydrogen, halogen, C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl or C₁ -C₄-haloalkyl, or a group --Y--R₅, --COOR₆, --NO₂ or --CO--NR₇ --R₈,

R₃ and R₄ independently of one another are hydrogen, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy,halogen or alkoxyalkyl having at most 4 carbon atoms,

R₅ and R₆ are each C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl or C₂ -C₆ -alkynyl,

R₇ and R₈ independently of one another are each hydrogen, C₁ -C₅ -alkyl,C₂ -C₅ -alkenyl or C₂ -C₆ -alkynyl, and

Y is oxygen, sulfur or a sulfinyl or sulfonyl bridge; and the inventionrelates also to the salts of these compounds.

Urea compounds, triazine compounds and pyrimidine compounds havingherbicidal activity are known in general. There have recently beendescribed arylsulfamoyl-heterocyclyl-aminocarbamoyl compounds having aherbicidal action and an action regulating plant growth, for example inthe European Patent Publications Nos. 1514 and 1515, in the U.S. Pat.No. 4,127,405, the German Offenlegungsschrift No. 2,715,786 and theFrench Patent Specification No. 1,468,747.

Alkyl in the definitions is straight-chain or branched-chain alkyl, forexample methyl, ethyl, n-propyl, i-propyl, the four isomeric butylgroups, n-amyl, i-amyl, 2-amyl, 3-amyl, n-hexyl or i-hexyl.

By alkoxy is meant: methoxy, ethoxy, n-propyloxy, i-propyloxy and thefour isomeric butyloxy groups, in particular however methoxy, ethoxy ori-propoxy.

Examples of alkylthio are: methylthio, ethylthio, n-propylthio,i-propylthio and n-butylthio, but especially methylthio and ethylthio.

Examples of alkenyl groups are: vinyl, allyl, isopropenyl, 1-propenyl,1-butenyl, 2-butenyl, 3-butenyl, 1-isobutenyl, 2-isobutenyl, 1-pentenyl,2-pentenyl, 3-pentenyl and 4-pentenyl, particularly however, vinyl,allyl and 4-pentenyl.

Examples of alkylsulfinyl are: methylsulfinyl, ethylsulfinyl,n-propylsulfinyl and n-butylsulfinyl, especially methylsulfinyl andethylsulfinyl.

Examples of alkylsulfonyl are: methylsulfonyl, ethylsulfonyl,n-propylsulfonyl and n-butylsulfonyl, particularly howevermethylsulfonyl and ethylsulfonyl.

Halogen in the definitions, as well as in haloalkyl, -alkoxy,-alkylsulfinyl, -alkylsulfonyl and -alkylthio, is fluorine, chlorine andbromine, preferably fluorine and chlorine.

Alkynyl groups in the definitions of the above symbols are as a rule:propargyl, 2-butynyl and 3-butynyl, as well as isomeric pentynyl orhexynyl groups; the alkynyl group is preferably however propargyl or 2-or 3-butynyl.

The invention embraces also the salts which the compounds of the formulaI can form with amines, alkali metal bases and alkaline-earth metalbases or quaternary ammonium bases. To be emphasised among the alkalimetal and alkaline-earth metal hydroxides as salt formers are thehydroxides of lithium, sodium, potassium, magnesium or calcium,especially however of sodium or potassium. Examples of amines suitablefor forming salts are: primary, secondary and tertiary aliphatic andaromatic amines, such as methylamine, ethylamine, propylamine,i-propylamine, the four isomeric butylamines, dimethylamine,diethylamine, diethanolamine, dipropylamine, diisopropylamine,di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine,triethylamine, tripropylamine, quinuclidine, pyridine, quinoline andi-quinoline, in particular however ethyl-, propyl-, diethyl- ortriethylamine, but especially isopropylamine and diethanolamine.Examples of quaternary ammonium bases are in general the cations ofhaloammonium salts, for example the tetramethylammonium cation, thetrimethylbenzylammonium cation, the triethylbenzylammonium cation, thetetraethylammonium cation or the trimethylethylammonium cation, but alsothe ammonium cation.

Preferred compounds of the formula I are those in which

(a) Z is oxygen, and

(b) R₃ and R₄ together contain no more than 4 carbon atoms.

The group (a) can be divided into two further subgroups consisting ofcompounds in which

(aa) m is the number one, and

(ab) m is the number two.

Preferred compounds from the group (aa) are those in which the group--X--A is in the 2- or 3-position with respect to the sulfonyl group.Compounds particularly preferred in this group are those wherein thegroup --X--A is in the 2-position.

A preferred group from the group (ab) is formed by the compounds inwhich the two --X--A groups are in the 2- and 5-positions with respectto the sulfonyl group.

A further preference with regard to compounds of the aforementionedsubgroups of the groups (aa) and (ab) is that R₃ and R₄ together containat most 4 carbon atoms. There are thus formed the especially preferredgroups of compounds of the formula I wherein

(aab) only one --X--A group is present in the 2-position with respect tothe sulfonyl group, Z is oxygen, and R₃ and R₄ together contain no morethan 4 carbon atoms atoms, and

(abb) two --X--A groups are present in the 2- and 5-position withrespect to the sulfonyl group, Z is oxygen, and R₃ and R₄ togethercontain no more than 4 carbon atoms.

Preferred compounds from the group (aab) are those in which R₁ ishydrogen, and R₂ is in the 5- or 6-position with respect to the sulfonylgroup. And of these compounds moreover, those are preferred in which R₂is hydrogen, halogen, C₁ -C₄ -alkoxy, nitro or COOR₆.

A further preference within the last-mentioned group is for thecompounds in which R₂ is hydrogen, fluorine, nitro or C₁ -C₄ -alkoxy,and R₃ and R₄ are each hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₁ -C₃ -haloalkoxy, halogen or alkoxyalkyl, where R₃ and R₄together contain no more than 4 carbon atoms.

Compounds among these which are in their turn preferred are those inwhich R₂ is hydrogen, and R₃ and R₄ are each C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, methylthio, 2,2,2-trifluoroethoxy, difluoromethoxy,1,1,2,2-tetrafluoroethoxy, halogen or alkoxyalkyl. A further preferencewithin the last-mentioned group is for the compounds in which X isoxygen or sulfur. More especially preferred of these, however, are thecompounds in which X is oxygen. Preferred compounds within this groupare those in which A is propargyl.

Of the compounds of the formula I wherein Z is sulfur, those arepreferred in which X is oxygen or sulfur, R₃ and R₄ independently of oneanother are each C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, C₁ -C₃ -alkylthio,difluoromethoxy or 2,2,2-trifluoroethoxy, with together at most 4 carbonatoms, and A is --CH₂ --C.tbd.CH, --CH₂ --C.tbd.C--CH₃ or --CH₂ --CH₂--C.tbd.CH, and the --X--A group occupies the 2-position, and m is thenumber 1.

The following are given as preferred individual compounds:

N-(2-propargyloxyphenyl-sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea,

N-(2-propargyloxyphenyl-sulfonyl)-N'-(4-ethyl-6-methoxy-1,3,5-triazin-2-yl)-urea,

N-(2-propargyloxyphenyl-sulfonyl)-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea,and

N-(2-propargyloxyphenyl-sulfonyl)-N'-(4-ethoxy-6-methyl-1,3,5-triazin-2-yl)-urea.

The compounds of the formula I are produced in an inert organic solvent.

One process for producing the compounds of the formula I comprisesreacting a phenylsulfonamide of the formula II ##STR3## wherein A, R₁,R₂, X and m have the meanings defined under the formula I, in thepresence of a base, with an N-pyrimidinyl- or -triazinylcarbamate of theformula III ##STR4## wherein E, R₃, R₄ and Z have the meanings definedunder the formula I.

Compounds of the formula I are obtained, using a second process, byreacting a phenylsulfonylisocyanate or -isothiocyanate of the formula IV##STR5## wherein A, R₁, R₂, m, X and Z are as defined under the formulaI, optionally in the presence of a base, with an amine of the formula V##STR6## wherein E, R₃ and R₄ have the meanings defined under theformula I.

Compounds of the formula I are produced in a further process by reactinga sulfonamide of the formula II given above, optionally in the presenceof a base, with an isocyanate or isothiocyanate of the formula VI##STR7## wherein E, R₃, R₄ and Z are as defined under the formula I.

Finally, the compounds of the formula I can be obtained also by reactingan N-phenylsulfonylcarbamate of the formula VII ##STR8## wherein A, R₁,R₂, m, X and Z have the meanings defined under the formula I, with anamine of the above formula V.

The resulting ureas of the formula I can if desired be converted, bymeans of amines, alkali metal or alkaline-earth metal hydroxides orquaternary ammonium bases, into addition salts. This is effected forexample by reaction with the equimolar amount of a base, and removal ofthe solvent by evaporation.

The starting materials of the formulae II, IV and VII are novel and canbe produced by the following methods.

The novel sulfonamides of the formula II which are used as intermediatesare obtained from the corresponding anilines by diazotisation andexchange of the diazo group for sulfur dioxide in the presence of acatalyst, such as copper-I chloride, in hydrochloric acid or aceticacid, and reaction of the formed phenylsulfonyl chloride with ammonia.

The compounds of the formula I can be obtained also by oxygen- orsulfur-alkynylation of hydroxy- or thiophenylsulfonamides with thecorresponding halides or sulfuric acid esters, or by reaction ofortho-halophenylsulfonamides with metal alcoholates or mercaptides, andoptionally by oxidation thereof with for example periodates or peroxyacids to the corresponding sulfoxides and sulfones.

Ortho-substituted hydroxyphenyl- or substitutedortho-hydroxyphenylsulfonamides of the formula VIII ##STR9## wherein R₁and R₂ have the meanings defined under the formula I, and X' is oxygenor sulfur, are known, as starting products of certain sulfonamiderepresentatives of the formula II, from the Swiss patent application No.3991/81-4. They can be obtained by ether cleavage of the correspondingC₁ -C₄ -alkoxyphenylsulfonamides for example with boron trihalides(reactions of this type are described in the U.S. Pat. No. 3,904,680 andin J. Am. Chem. Soc. 64, 1128 (1942)), or by hydrogenolysis of thecorresponding benzyloxyphenylsulfonamides, as described in J. Chem. Soc.1958, 2903.

The alkoxyphenylsulfonamides for their part can be obtained from thecorresponding alkoxyanilides, as already mentioned, or bychlorosulfonylation of alkoxybenzenes by reaction of the resultingphenylsulfonyl chlorides with ammonia. Such reactions have become knownfrom J. Am. Chem. Soc. 62, 603 (1940).

The compounds of the formula II and VII used as intermediates are noveland were developed specifically for the synthesis of compounds of theformula I. These intermediates form further subject matter of thepresent invention.

The phenylsulfonylisocyanates of the formula IV can be obtained byreaction of the sulfonamides of the formula II with phosgene in thepresence of butylisocyanate, in a chlorinated hydrocarbon as solvent, atreflux temperature. Similar production methods are described in "NeuereMethoden der praparativen organischen Chemie", Vol. VI, 211-229, VerlagChemie, Weinheim, 1970.

The isothiocyanates of the formula IV are obtained by treatment of thesulfonamides of the formula II with carbon disulfide and potassiumhydroxide, and subsequent reaction of the dipotassium salt withphosgene. Processes of this kind are described in Arch. Pharm. 299, 174(1966).

The N-phenylsulfonylcarbamates of the formula VII are obtained byreaction of the sulfonamides of the formula II with diphenylcarbonate inthe presence of a base. Similar processes are mentioned in the JapanesePatent Specification No. 61 169.

The starting materials of the formulae III, V and VI are in part known.New compounds of the formulae III and VI can be obtained, by knownmethods, from corresponding compounds of the formula V.

New fluoroalkoxy-aminopyrimidines and -triazines of the formula V andthe production thereof, and also the production therefrom ofcorresponding compounds of the formulae III and VI, are described in theSwiss patent application No. 3527/82-8.

Isocyanates of the formula VI can be produced by reaction of amines ofthe formula V with oxalyl chloride in chlorinated hydrocarbons assolvents. Amines of the formula V are known and some are obtainablecommercially, or they can be produced by known methods (cp. "TheChemistry of Heterocyclic Compounds", Vol. XIV, Interscience Publishers,New York, London.

These reactions to give compounds of the formula I are advantageouslyperformed in aprotic, inert, organic solvents, such as methylenechloride, tetrahydrofuran, acetonitrile, dioxane and toluene.

The reaction temperatures are preferably between -20° and +120° C. Thereactions proceed in general slightly exothermically, and can be carriedout at room temperature. For the purpose of shortening the reaction timeor for initiating the reaction, it is advantageous to apply heat for ashort time up to the boiling point of the reaction mixture. The reactiontimes can be shortened also by the addition of some drops of a base orof isocyanate as a reaction catalyst.

The final products can be isolated by concentration by evaporationand/or by removal of the solvent by evaporation, and purified byrecrystallisation or trituration of the solid residue in solvents inwhich they do not readily dissolve, such as ether, aromatic hydrocarbonsor chlorinated hydrocarbons.

The active substances of the formula I are stable compounds, and thehandling of them necessitates no special precautions being taken.

In smaller applied amounts, the compounds of the formula I arecharacterised by good selective growth-inhibiting and selectiveherbicidal properties, which render them excellently suitable for use incrops of useful plants, especially in crops of cereals, cotton,soya-bean, maize and rice. The preferred crops are cereals, such aswheat, barley and rye. Also destroyed in some cases are weeds whichhitherto could be dealt with only by the use of total herbicides.

The mode of action of these active substances is unusual. Many arecapable of being translocated, that is to say, they are taken up by theplant and transported to other locations, where they produce the desiredeffect. It is thus possible for example by surface treatment ofperennial weeds to destroy them at their roots. The novel compounds ofthe formula I are effective in applied amounts which are very smallcompared with the amounts required to obtain the same effect using otherherbicides and plant-growth regulators.

The compounds of the formula I also have excellent properties forregulating, especially reducing, plant growth. Both monocotyledons anddicotyledons are impaired in their growth. A reduction of the vegetativegrowth enables in the case of many cultivated plants the crop density tobe raised, so that higher yields for the same area of land can beachieved.

An additional factor contributing to the increase in yield with the useof growth inhibitors is that the formation of blossom and fruit benefitsto a greater extent from the nutritive substances, because thevegetative growth is restricted.

Thus, for example, the leguminosae frequently planted as cover crops inagriculture in tropical regions are selectively inhibited in theirgrowth by the compounds of the formula I, the result being that soilerosion between the cultivated plants is prevented, without the covercrops being able to compete with the main cultivated crop.

Furthermore, the compounds of the formula I are suitable for preventingthe sprouting of stored potatoes. Shoots frequently form on potatoesbeing stored during the winter, and the shoots cause shrinkage, loss inweight and rotting.

With larger applied amounts of active substance, all the tested plantswere impaired in their development to the extent that they died.

The invention relates also to herbicidal and plantgrowth-regulatingcompositions containing a novel active ingredient of the formula I, andalso to processes for the pre- and post-emergence combating of weeds,and for the reduction of growth of monocotyledonous and dicotyledonousplants, particularly that of grasses, tropical cover crops and sideshoots of tobacco plants.

The compounds of the formula I are used either in an unmodified form orpreferably in compositions, together with auxiliaries customarilyemployed in formulation practice, and are thus processed, in a knownmanner, for example into the form of emulsion concentrates, directlysprayable or dilutable solutions, diluted emulsions, wettable powders,soluble powders, dusts or granulates, and also encapsulations in forexample polymeric substances. The application processes, such asspraying, atomising, dusting, scattering or pouring, and likewise thetype of composition, are selected to suit the objects to be achieved andthe given conditions.

The formulations, that is to say, the compositions or preparationscontaining the active ingredient of the formula I and optionally a solidor liquid additive, are produced in a known manner, for example by theintimate mixing and/or grinding of the active ingredients withextenders, such as with solvents, solid carriers and optionallysurface-active compounds (tensides).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionsC₈ to C₁₂, such as xylene mixtures or substituted naphthalenes, phthalicesters, such as dibutyl- or dioctylphthalate, aliphatic hydrocarbons,such as cyclohexane or paraffins, alcohols and glycols, as well asethers and esters thereof, such as ethanol, ethylene glycol, ethyleneglycol monomethyl or -ethyl ethers, ketones, such as cyclohexanone,strongly polar solvents, such as N-methyl-2-pyrrolidone,dimethylsulfoxide or dimethylformamide, as well as optionally epoxidisedvegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, for example for dusts and dispersible powders,are as a rule natural mineral fillers, such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties, it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, ground brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. There can also be used a great number of pre-granulatedmaterials of inorganic or organic nature, such as in particular dolomiteor ground plant residues.

Suitable surface-active compounds are, depending on the nature of theactive substance of the formula I to be formulated, nonionic, cationicand/or anionic tensides having good emulsifying, dispersing and wettingproperties. By `tensides` are also meant mixtures of tensides.

Suitable anionic tensides are both so-called water-soluble soaps as wellas water-soluble, synthetic, surface-active compounds.

Soaps which are applicable are the alkali metal, alkaline-earth metal oroptionally substituted ammonium salts of higher fatty acids (C₁₀ -C₂₂),for example the Na or K salts of oleic or stearic acid, or of naturalfatty acid mixtures, which can be obtained for example from coconut oilor tallow oil. Also to be mentioned are the fatty acid-methyl-taurinesalts.

So-called synthetic tensides are however more frequently used,particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates. The fatty sulfonates or sulfates areas a rule in the form of alkali metal, alkaline-earth metal oroptionally substituted ammonium salts, and contain an alkyl group having8 to 22 C atoms, `alkyl` including also the alkyl moiety of acyl groups,for example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuricacid ester or of a fatty alcohol sulfate mixture produced from naturalfatty acids. Included among these are also the salts of sulfuric acidesters and sulfonic acids of fatty alcohol ethylene oxide adducts. Thesulfonated benzimidazole derivatives preferably contain 2 sulfonic acidgroups and a fatty acid group having 8-22 C atoms. Alkylarylsulfonatesare for example the Na, Ca or triethanolamine salts ofdodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of anaphthalenesulfonic acid-formaldehyde condensation product. Alsosuitable are corresponding phosphates, for example salts of thephosphoric ester of a p-nonylphenol-(4`-14)-ethylene oxide adduct.

Suitable nonionic tensides are in particular polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, saturated orunsaturated fatty acids and alkylphenols, which can contain 3 to 30glycol ether groups and 8 to 20 carbon atoms in the (aliphatic)hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of thealkylphenols.

Further suitable nonionic tensides are the water-soluble polyethyleneoxide adducts, which contain 20 to 250 ethylene glycol ether groups and10 to 100 propylene glycol ether groups, with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usuallycontain 1 to 5 ethylene glycol units per propylene glycol unit. Examplesof nonionic tensides which may be mentioned are:nonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethyleneoxy adducts, tributylphenoxypolyethoxyethanol,polyethylene glycol and octylphenoxypolyethoxyethanol. Suitable also arefatty acid esters of polyoxyethylenesorbitan, such aspolyoxyethylene-sorbitan-trioleate.

In the case of the cationic tensides, they are in particular quaternaryammonium salts which contain as N-substituents at least one alkyl grouphaving 8 to 22 C atoms and, as further substituents, lower, optionallyhalogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts arepreferably in the form of halides, methyl sulfates or ethyl sulfates,for example stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The tensides customarily used in formulation practice are described,inter alia, in the following publications: "Mc Cutcheon's Detergents andEmulsifiers Annual" MC Publishing Corp., Ridgewood, N.J., 1979; andSisley and Wood, "Encyclopedia of Surface Active Agents", ChemicalPublishing Co., Inc. New York, 1964.

The agrochemical preparations contain as a rule 0.1 to 95%, especially0.1 to 80%, of active ingredient of the formula I, 1 to 99.9% of a solidor liquid additive, and 0 to 25%, particularly 0.1 to 25%, of a tenside.

Preferred formulations are made up in particular as follows (%=percentby weight):

    ______________________________________                                        Emulsifiable concentrates                                                     active ingredient:                                                                           1 to 20%, preferably 5 to 10%                                  surface active agent:                                                                        5 to 30%, preferably 10 to 20%                                 liquid carrier:                                                                              50 to 94%,                                                                              preferably 70 to 85%.                                Dusts                                                                         active ingredient:                                                                           0.1 to 10%,                                                                             preferably 0.1 to 1%                                 solid carrier: 99.9 to 90%                                                                             preferably 99.9 to 99%.                              Suspension concentrates                                                       active ingredient:                                                                           5 to 75%, preferably 10 to 50%                                 water:         94 to 25%,                                                                              preferably 90 to 30%                                 surface-active agent:                                                                        1 to 40%, preferably 2 to 30%.                                 Wettable powders                                                              active ingredient:                                                                           0.5 to 90%,                                                                             preferably 1 to 80%                                  surface-active agent:                                                                        0.5 to 20%,                                                                             preferably 1 to 15%                                  solid carrier: 5 to 95%, preferably 15 to 90%.                                Granulates                                                                    active ingredient:                                                                           0.5 to 30%,                                                                             preferably 3 to 15%                                  solid carrier: 99.5 to 70%,                                                                            preferably 97 to 85%.                                ______________________________________                                    

Whereas commercial products are preferably in the form of concentratedcompositions, the compositions employed by the end-user are as a rulediluted. The preparations can for application be diluted down to 0.001%of active ingredient. The applied amounts are usually 0.01 to 10 kg,preferably 0.025 to 5, kg of active substance per hectare.

The compositions can also contain additives such as stabilisers,antifoaming agents, viscosity regulators, binders and adhesives, as wellas fertilisers or other active substances for obtaining special effects.

In the following Examples, the temperatures are given in degreesCentigrade (°C.), and pressures in millibars (mb).

PRODUCTION EXAMPLES EXAMPLE 1 (a) 2-Propargyloxyphenylsulfonamide:

A mixture of 35 g of 2-hydroxyphenylsulfonamide, 55.2 g of potassiumcarbonate, 15.5 ml of propargyl bromide and 1000 ml of ethyl methylketone is refluxed for 1.5 hours; it is then cooled, filtered, andconcentrated by evaporation. The yield after recrystallisation of theresidue from ethyl acetate is 30 g of 2-propargyloxyphenylsulfonamide,m.p. 143°-145° C.

(b) N-(2-Propargyloxyphenylsulfonyl)-phenyl carbamate:

A solution of 15.1 g of 2-propargyloxyphenylsulfonamide in 100 ml ofdimethylformamide is added dropwise within 10 minutes, at a maximumtemperature of 10° C. in a nitrogen atmosphere, to the suspension of3.09 g of 55% sodium hydride in 30 ml of absolute dimethylformamide. Thereaction mixture is stirred for 15 minutes at room temperature; there issubsequently added dropwise, in the course of 20 minutes, a solution of15.94 g of diphenyl carbonate in 100 ml of dimethylformamide, and themixture is stirred for a further 45 minutes. The reaction mixture isafterwards taken up in a mixture of 600 g of ice, 90.5 ml of 2Nhydrochloric acid and 600 ml of ethyl acetate. The organic phase iswashed twice with ice water, dried over sodium sulfate and concentratedby evaporation. Ether/petroleum ether (1:1) is added to the oily residueto thus obtain 21.4 g of crystallineN-(2-propargyloxyphenylsulfonyl)-phenyl carbamate, m.p. 155°-157° C.

(c)N-(2-Propargyloxyphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea:

A mixture of 3.33 g of N-(2-propargyloxyphenylsulfonyl)-phenyl carbamateand 1.4 g of 2-amino-4-methoxy-6-methyl-1,3,5-triazine in 30 ml ofabsolute dioxane is refluxed for 45 minutes; the mixture is then cooledto room temperature, filtered, and concentrated by evaporation. Theyield after trituration of the residue with 40 ml of ether is 2.38 g ofcrystallineN-(2-propargyloxyphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea,m.p. 157°-158° C.

EXAMPLE 2 (a) 5-Methyl-2-propargyloxyphenylsulfonamide:

A mixture of 24.3 g of 2-hydroxy-5-methylphenylsulfonamide, 36.0 g ofpotassium carbonate, 16.7 g of propargyl bromide and 500 ml ofacetonitrile is stirred at 50° C. for 4.5 hours. The reaction mixture isthen filtered, and concentrated by evaporation. The yield afterrecrystallisation from ethyl acetate is 23.9 g of5-methyl-2-propargyloxyphenylsulfonamide, m.p. 169°-170° C.

(b) 5-Methyl-2-propargyloxyphenylsulfonylisocyanate:

A mixture of 22.4 g of 5-methyl-2-propargyloxyphenylsulfonamide, 9.9 gof n-butylisocyanate, 0.3 g of 1,4-diazabicyclo(2,2,2)octane and 350 mlof absolute xylene is refluxed for 30 minutes; and about 20 g ofphosgene are subsequently introduced at 115°-120° C. during 2 hours.After the excess of phosgene has been removed from the reaction mixtureby feeding in nitrogen, the mixture is cooled to room temperature,filtered, and concentrated in vacuo. There is thus obtained as crudeproduct 28.1 g of 5-methyl-2-propargyloxyphenylsulfonylisocyanate in theform of brown oil. This crude product is used, without furtherpurification, in the subsequent stage.

(c)N-(5-Methyl-2-propargyloxyphenylsulfonyl)-N'-(4-chloro-6-methoxypyrimidin-2-yl)-urea:

A solution of 9.4 g of crude5-methyl-2-propargyloxyphenylsulfonylisocyanate in 50 ml of absolutetetrahydrofuran is added dropwise at room temperature, within 10minutes, to a solution of 3.7 g of 2-amino-4-chloro-6-methoxy-pyrimidineand 0.1 g of 1,4-diazadicyclo[2.2.2]-octane in 60 ml of absolutetetrahydrofuran, in the course of which the temperature rises slightly.The reaction solution is stirred for 18 hours at room temperature; it isthen filtered, and concentrated by evaporation. The residue iscrystallised from ethyl acetate to thus obtain 5.8 g ofN-(5-methyl-2-propargyloxyphenylsulfonyl)-N'-(4-chloro-6-methoxy-pyrimidin-2-yl)-urea,m.p. 202°-204° C.

The intermediate and final products listed in the following Tables areobtained in an analogous manner.

                                      TABLE 1                                     __________________________________________________________________________     ##STR10##                                                                                                 Position                                                                           Physical                                    R.sub.1 R.sub.2                                                                             X  A           of XA                                                                              data                                        __________________________________________________________________________    H       H     O  CH.sub.2CCH 2    m.p. 143-145°                        H       H     S  CH.sub.2CCH 2                                                H       H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                H       H     O  CH.sub.2CCCH.sub.3                                                                        2                                                6-Cl    H     O  CH.sub.2CCH 2                                                6-Cl    H     O  CH.sub.2CCH.sub.3                                                                         2                                                6-Cl    H     O  CH.sub.2CH.sub.2C CH                                                                      2                                                6-OCH.sub.3                                                                           H     O  CH.sub.2CCH 2                                                6-OCH.sub.3                                                                           H     O  CH.sub.2CCCH.sub.3                                                                        2                                                6-CH.sub.3                                                                            H     O  CH.sub.2CCH 2                                                6-CH.sub.3                                                                            H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                6-NO.sub.2                                                                            H     O  CH.sub.2CCH 2                                                6-NO.sub.2                                                                            H     O  CH.sub.2CCCH.sub.3                                                                        2                                                6-COOCH.sub.3                                                                         H     O  CH.sub.2CCH 2                                                5-Cl    H     O  CH.sub.2CCH 2    m.p. 145°                            5-Cl    H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-Cl    H     O  CH.sub.2C CCH.sub.3                                                                       2                                                5-Br    H     O  CH.sub.2CCH 2                                                5-Br    H     O  CH.sub.2CCCH.sub.3                                                                        2                                                5-Br    H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-F     H     O  CH.sub.2CCH 2    m.p. 156-157°                        5-F     H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-F     H     O  CH.sub.2CCCH.sub.3                                                                        2                                                5-CH(CH.sub.3).sub.2                                                                  H     O  CH.sub.2CCH 2                                                5-CH(CH.sub.3).sub.2                                                                  H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-CH(CH.sub.3).sub.2                                                                  H     O  CH.sub.2CCCH.sub.3                                                                        2                                                5-CH.sub.3                                                                            H     O  CH.sub.2CCH 2    m.p. 169-171°                        5-CH.sub.3                                                                            H     O  CH.sub.2CCCH.sub.3                                                                        2                                                5-CH.sub.3                                                                            H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-NO.sub.2                                                                            H     O  CH.sub.2CCH 2                                                5-NO.sub.2                                                                            H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-NO.sub.2                                                                            H     O  CH.sub.2CCCH.sub.3                                                                        2                                                5-OCH.sub.3                                                                           H     O  CH.sub.2CCCH.sub.3                                                                        2                                                5-OCH.sub.3                                                                           H     O  CH.sub.2CCH 2                                                5-OCH.sub.3                                                                           H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-CON(CH.sub.3).sub.2                                                                 H     O  CH.sub.2C CH                                                                              2                                                5-CON(CH.sub.3).sub.2                                                                 H     O  CH.sub.2CCCH.sub.3                                                                        2                                                5-COOCH.sub.3                                                                         H     O  CH.sub.2CCH 2                                                5-COOCH.sub.3                                                                         H     O  CH.sub.2CCCH.sub.3                                                                        2                                                5-COOCH.sub.3                                                                         H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-NO.sub.2                                                                            3-CF.sub.3                                                                          O  CH.sub.2CCH 2                                                5-NO.sub.2                                                                            3-Cl  O  CH.sub.2CCH 2                                                5-NO.sub.2                                                                            3-Cl  O  CH.sub.2CCCH.sub.3                                                                        2                                                5-CF.sub.3                                                                            3-NO.sub.2                                                                          O  CH.sub.2CCH 2                                                5-CH.sub.3                                                                            3-CH.sub.3                                                                          O  CH.sub.2CCH 2                                                5-CH.sub.3                                                                            3-CH.sub.3                                                                          O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-Cl    3-NO.sub.2                                                                          O  CH.sub.2C CH                                                                              2                                                5-Cl    3-Cl  O  CH.sub.2CCH 2                                                5-Cl    3-Cl  O  CH.sub.2CCCH.sub.3                                                                        2                                                5-Cl    3-Cl  O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-Br    3-OCH.sub.3                                                                         O  CH.sub.2CCH 2                                                5-Br    2-OCH.sub.3                                                                         O  CH.sub.2CCH 3                                                3-OCH.sub.3                                                                           5-COOCH.sub.3                                                                       O  CH.sub.2CCH 2                                                2-OCH.sub.3                                                                           5-COOCH.sub.3                                                                       O  CH.sub.2CCH 3                                                5-CH.sub.3                                                                            3-Br  O  CH.sub.2CCH 2                                                5-Br    3-NO.sub.2                                                                          O  CH.sub.2CCH 2                                                5-Cl    3-Br  O  CH.sub.2CCH 2                                                5-Cl    3-Br  O  CH.sub.2CCCH.sub.3                                                                        2                                                5-Cl    3-Br  O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-CH(CH.sub.3).sub.2                                                                  3-CH.sub.3                                                                          O  CH.sub.2CH.sub.2CCH                                                                       2                                                5-CH(CH.sub.3).sub.2                                                                  3-CH.sub.3                                                                          O  CH.sub.2CCCH.sub.3                                                                        2                                                5-CH(CH.sub.3).sub.2                                                                  3-CH.sub.3                                                                          O  CH.sub.2CCH 2                                                3-NO.sub.2                                                                            H     O  CH.sub.2CCH 2                                                3-CH.sub.3                                                                            H     O  CH.sub.2CCH 2                                                3-NO.sub.2                                                                            H     O  CH.sub.2CCH 2                                                3-Cl    H     O  CH.sub.2CCH 2                                                3-Cl    H     O  CH.sub.2C CCH.sub.3                                                                       2                                                3-Cl    H     O  CH.sub.2CH.sub.2CCH                                                                       2                                                3-OCH.sub.3                                                                           H     O  CH.sub.2CCH 2                                                3-OCH.sub.3                                                                           H     O  CH.sub.2CCCH.sub.3                                                                        2                                                2-OCH.sub.3                                                                           H     O  CH.sub.2CCH 2                                                H       H     SO CH.sub.2CCH 2                                                H       H     SO.sub.2                                                                         CH.sub.2CCH 2                                                H       H     SO CH.sub.2CCCH.sub.3                                                                        2                                                H       H     SO.sub.2                                                                         CH.sub.2CCCH.sub.2                                                                        2                                                2-Cl    H     O  CH.sub.2CCH 5    m.p. 149°                            6-Cl    4-Br  O  CH.sub.2C CH                                                                              3    m.p. 174°                            __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR11##                                                                    No.                                                                              A           R.sub.3 R.sub.4       X  E  Physical data                      __________________________________________________________________________    1  CH.sub.2CCH CH.sub.3                                                                              C.sub.2 H.sub.5                                                                             S  N                                     2  CH.sub.2CCH OCH.sub.3                                                                             C.sub.2 H.sub.5                                                                             S  N                                     3  CH.sub.2CCH CH.sub.3                                                                              OCH.sub.3     S  CH                                    4  CH.sub.2CCH OCH.sub.3                                                                             OCH.sub.3     S  CH                                    5  CH.sub.2C CH                                                                              CH.sub.3                                                                              OCH.sub.3     SO N                                     6  CH.sub.2CCH OCH.sub.3                                                                             OCH.sub.3     SO N                                     7  CH.sub.2CCH OCH.sub.3                                                                             c.sub.2 H.sub.5                                                                             SO N                                     8  CH.sub.2CCH CH(CH.sub.3).sub.2                                                                    OCH.sub.3     O  CH m.p. 129-130°               9  CH.sub.2CCH OCH.sub.3                                                                             SC.sub.2 H.sub.5                                                                            O  CH                                    10 CH.sub.2CCH OCH.sub.3                                                                             SC.sub.2 H.sub.5                                                                            O  N                                     11 CH.sub.2CCH OCH.sub.3                                                                             SCH(CH.sub.3).sub.2                                                                         O  N                                     12 CH.sub.2CCH CCl     CH.sub.3      O  N  m.p. 179-180°               13 CH.sub.2CCH CH.sub.3                                                                              Br            O  N                                     14 CH.sub.2C CH                                                                              CHF.sub.3                                                                             CH.sub.3      O  N                                     16 CH.sub.2CCH OCH.sub.2 CF.sub.3                                                                    Cl            O  N                                     17 CH.sub.2CCH OCH.sub.2 CF.sub.3                                                                    OCH.sub.3     O  N  m.p. 113-115°               18 CH.sub.2CCH CH.sub.2 CF.sub.3                                                                     CH.sub.3      O  N                                     19 CH.sub.2CCH OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                            O  N  m.p. 138-139°               20 CH.sub.2CCH OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                            O  CH                                    21 CH.sub.2CCH C.sub.2 H.sub.5                                                                       OCH.sub.3     O  N  m.p. 134-135°               22 CH.sub.2CCH C.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                            O  N                                     23 CH.sub.2C CH                                                                              CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                            O  N  m.p. 129-130°               24 CH.sub.2CCH CH.sub.3                                                                              CH.sub.3      O  CH                                    25 CH.sub.2CCH CH.sub.3                                                                              OCH.sub.3     O  CH m.p. 156-159°               26 CH.sub.2CCH CH.sub.3                                                                              OCH.sub.2CF.sub.3                                                                           O  N                                     27 CH.sub.2CCH CH.sub.3                                                                              H             O  N  m.p. 186-187°               28 CH.sub.2CCH C.sub.2 H.sub.5                                                                       Cl            O  CH                                    29 CH.sub.2CCH CH.sub.3                                                                              Cl            O  CH m.p. 225-227°               30 CH.sub.2CCH CH.sub.3                                                                              SCH.sub.3     O  CH                                    31 CH.sub.2CCH CH.sub.3                                                                              F             O  CH                                    32 CH.sub.2C CH                                                                              CH.sub.3                                                                              Br            O  CH                                    33 CH.sub.2CCH C.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                            O  CH                                    34 CH.sub.2CCH C.sub.2 H.sub.5                                                                       SCH.sub.3     O  CH                                    35 CH.sub.2CCH CF.sub.3                                                                              CH.sub.3      O  CH                                    36 CH.sub.2CCH CH.sub.2 Cl                                                                           CH.sub.3      O  CH                                    37 CH.sub.2CCH CH.sub.2 Cl                                                                           OCH.sub.3     O  CH                                    38 CH.sub.2C CH                                                                              OCH.sub.3                                                                             Cl            O  CH m.p. 209-210°               39 CH.sub.2CCH Cl      Cl            O  CH                                    40 CH.sub.2CCH OCH.sub.3                                                                             SCH.sub.3     O  CH                                    41 CH.sub.2CCH OCH.sub.3                                                                             OCH(CH.sub.3).sub.2                                                                         O  CH                                    42 CH.sub.2CCH CH.sub.2 F                                                                            OCH.sub.3     O  CH                                    43 CH.sub.2CCH CHF.sub.2                                                                             CH.sub.3      O  CH m.p. 189-192°               44 CH.sub.2CCH CF.sub.3                                                                              OCH.sub.3     O  CH                                    45 CH.sub.2CCH C.sub.2 H.sub.5                                                                       OCH(CH.sub.3).sub.2                                                                         O  N                                     46 CH.sub.2CCH C.sub.2 H.sub.5                                                                       Cl            O  N                                     47 CH.sub.2CCH C.sub.2 H.sub.5                                                                       SCH.sub.3     O  N                                     48 CH.sub.2CCH C.sub.2 H.sub.5                                                                       CH.sub.3      O  N  m.p. 132-134°               49 CH.sub.2C CH                                                                              C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             O  N                                     50 CH.sub.2CCH OCH.sub.3                                                                             OCH(CH.sub.3).sub.2                                                                         O  N  m.p. 93-95°                 51 CH.sub.2CCH OCH.sub.3                                                                             OCH(CH.sub.3)CH.sub.2CH.sub.3                                                               O  N                                     52 CH.sub.2CCH CH.sub.3                                                                              CH(CH.sub.3).sub.2                                                                          O  N                                     53 CH.sub.2CCH CH(CH.sub.3).sub.2                                                                    Cl            O  N  m.p. 120-121°               54 CH.sub.2CCH CH(CH.sub.3).sub.2                                                                    OCH.sub.3     O  N                                     55 CH.sub.2CCH CH(CH.sub.3).sub.2                                                                    OC.sub.2 H.sub.5                                                                            O  N                                     56 CH.sub.2CCH CH(CH.sub.3).sub.2                                                                    SCH.sub.3     O  N                                     57 CH.sub. 2CCH                                                                              CH.sub.2 Cl                                                                           CH.sub.3      O  N                                     58 CH.sub.2CCH CH.sub.2 Cl                                                                           OCH.sub.3     O  N                                     59 CH.sub.2CCH CH.sub.2 F                                                                            CH.sub.3      O  N                                     60 CH.sub.2CCH CH.sub.2 F                                                                            OCH.sub.3     O  N                                     61 CH.sub.2CCH CH.sub.2F                                                                             OC.sub.2 H.sub.5                                                                            O  N                                     62 CH.sub.2CCH CH.sub.2OCH.sub.3                                                                     C.sub.2 H.sub.5                                                                             O  N                                     63 CH.sub.2CCH CH.sub.2SCH.sub.3                                                                     OCH.sub.3     O  N                                     64 CH.sub.2CCH CH.sub.2SCH.sub.3                                                                     CH.sub.3      O  N                                     65 CH.sub.2 CCH                                                                              CH.sub.2SCH.sub.3                                                                     SCH.sub.3     O  N                                     66 CH.sub.2CCH CH.sub.2SCH.sub.3                                                                     Cl            O  N                                     67 CH.sub.2CCH CH.sub.2SCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                            O  N                                     68 CH.sub.2CCH SCH.sub.3                                                                             Cl            O  N  m.p. 139-140°               69 CH.sub.2CCH SCH.sub.3                                                                             OCH.sub.3     O  N                                     70 CH.sub.2CCH SCH.sub.3                                                                             C.sub.2 H.sub.5                                                                             O  N                                     71 CH.sub.2CCH SCH.sub.3                                                                             OCH(CH.sub.3).sub.2                                                                         O  N                                     72 CH.sub.2CCH OCH(CH.sub.3).sub.2                                                                   Cl            O  N                                     73 CH.sub.2CCH CF.sub. 3                                                                             OCH.sub.3     O  N                                     74 CH.sub.2CCH CF.sub.3                                                                              CH.sub.3      O  N                                     75 CH.sub.2CCH CF.sub.3                                                                              OC.sub.2 H.sub.5                                                                            O  N                                     76 CH.sub.2CCH CCl     OCH.sub.3     O  N                                     77 CH.sub.2CCH CCl.sub.3                                                                             SCH.sub.3     O  N                                     78 CH.sub.2CCH CH.sub.3                                                                              Cl            O  N                                     79 CH.sub.2CCH OCH.sub.3                                                                             Cl            O  N  m.p. 148-154°               80 CH.sub.2CCH OCH.sub.3                                                                             F             O  N                                     81 CH.sub.2CCH OCH.sub.3                                                                             Br            O  N                                     82 CH.sub.2CCH CH.sub.3                                                                              F             O  N                                     83 CH.sub.2C CH                                                                              OCH.sub.3                                                                             OCH.sub.3     O  CH                                    84 CH.sub.2CCH CH.sub.3                                                                              CH.sub.3      O  N  m.p. 175-177°               85 CH.sub.2CCH OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                            O  N                                     86 CH.sub.2CCH OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                            O  CH                                    87 CH.sub.2CCH CH.sub.2OCH.sub.3                                                                     OCH.sub.3     O  CH m.p. 162-163°               88 CH.sub.2CCH CH.sub.2OCH.sub.3                                                                     OCH.sub.3     O  N                                     89 CH.sub.2CCH C.sub.2 H.sub.5                                                                       OCH.sub.3     O  CH                                    90 CH.sub.2CCH CH.sub.2OCH.sub.3                                                                     CH.sub.3      O  N                                     91 CH.sub.2CCH CH.sub.3                                                                              OCH.sub.3     S  N                                     92 CH.sub.2CCH OCH.sub.3                                                                             OCH.sub.3     S  N                                     93 CH.sub.2CCH CH.sub.3                                                                              OCH.sub.3     O  N  m.p. 157-158°               94 CH.sub.2 CCH                                                                              OCH.sub.3                                                                             OCH.sub.3     O  N  m.p. 130-132°               95 CH.sub.2CCCH.sub.3                                                                        CH.sub.2 Cl                                                                           OCH.sub.3     O  N                                     96 CH.sub.2CCCH.sub.3                                                                        CH.sub.2 F                                                                            OCH.sub.3     O  N                                     97 CH.sub.2CCCH.sub.3                                                                        CH.sub.3                                                                              OCH.sub.3     O  CH                                    98 CH.sub.2CCCH.sub.3                                                                        OCH.sub.3                                                                             OCH.sub.3     O  CH                                    99 CH.sub.2CCCH.sub.3                                                                        CH.sub.3                                                                              CH.sub.3      O  CH                                    100                                                                              CH.sub.2C CCH.sub.3                                                                       C.sub.2 H.sub.5                                                                       OCH.sub.3     O  CH                                    101                                                                              CH.sub.2CCCH.sub.3                                                                        OCH.sub.3                                                                             Cl            O  CH                                    102                                                                              CH.sub.2CCCH.sub.3                                                                        CH.sub.3                                                                              Cl            O  CH                                    103                                                                              CH.sub.2CCCH.sub.3                                                                        CF.sub.3                                                                              OCH.sub.3     O  CH                                    104                                                                              CH.sub.2CCCH.sub.3                                                                        CH.sub.2OCH.sub.3                                                                     OCH.sub.3     O  CH                                    105                                                                              CH.sub.2CCCH.sub.3                                                                        Br      OCH.sub.3     O  CH                                    106                                                                              CH.sub.2CCCH.sub.3                                                                        Br      CH.sub.3      O  CH                                    107                                                                              CH.sub.2CCCH.sub.3                                                                        OCH.sub.3                                                                             SCH.sub.3     O  CH                                    108                                                                              CH.sub.2CCCH.sub.3                                                                        CH.sub.3                                                                              SCH.sub. 3    O  CH                                    109                                                                              CH.sub.2CCCH.sub.3                                                                        OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                            O  CH                                    110                                                                              CH.sub.2CCCH.sub.3                                                                        CH.sub.3                                                                              CH.sub.3      O  N                                     111                                                                              CH.sub.2CCCH.sub.3                                                                        CH.sub.3                                                                              OCH.sub.3     O  N                                     112                                                                              CH.sub.2CCCH.sub.3                                                                        OCH.sub.3                                                                             OCH.sub.3     O  N                                     113                                                                              CH.sub.2CCCH.sub.3                                                                        OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                            O  N                                     114                                                                              CH.sub.2CCCH.sub.3                                                                        C.sub.2 H.sub.5                                                                       OCH.sub.3     O  N                                     115                                                                              CH.sub.2CCCH.sub.3                                                                        C.sub.2 H.sub.5                                                                       CH.sub.3      O  N                                     116                                                                              CH.sub.2CCCH.sub.3                                                                        Cl      OCH.sub.3     O  N                                     117                                                                              CH.sub.2C CCH.sub.3                                                                       OCH(CH.sub.3).sub.2                                                                   OCH.sub.3     O  N                                     118                                                                              CH.sub.2CCCH.sub.3                                                                        OCH(CH.sub.3).sub.2                                                                   OCH.sub.3     O  N                                     119                                                                              CH.sub.2CCCH.sub.3                                                                        OCH(CH.sub.3).sub.2                                                                   CH.sub.3      O  N                                     120                                                                              CH.sub.2CCCH.sub.3                                                                        OCH.sub.3                                                                             SCH.sub.3     O  N                                     121                                                                              CH.sub.2CCCH.sub.3                                                                        OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                            O  N                                     122                                                                              CH.sub.2CCCH.sub.3                                                                        OCH.sub.3                                                                             CH.sub.2OCH.sub.3                                                                           O  N                                     123                                                                              CH.sub.2CH.sub.2CCH                                                                       CH.sub.3                                                                              OCH.sub.3     O  N                                     124                                                                              CH.sub.2CH.sub.2CCH                                                                       CH.sub.3                                                                              CH.sub.3      O  N                                     125                                                                              CH.sub.2CH.sub.2 CCH                                                                      C.sub.2 H.sub.5                                                                       OCH.sub.3     O  N                                     126                                                                              CH.sub.2CH.sub.2CCH                                                                       C.sub.2 H.sub.5                                                                       CH.sub.3      O  N                                     127                                                                              CH.sub.2CH.sub.2CCH                                                                       OCH.sub.3                                                                             OCH.sub.3     O  N                                     128                                                                              CH.sub.2CH.sub.2CCH                                                                       OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                            O  N                                     129                                                                              CH.sub.2CH.sub.2CCH                                                                       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                            O  N                                     130                                                                              CH.sub.2CH.sub.2CCH                                                                       CH.sub.2OCH.sub.3                                                                     OCH.sub.3     O  N                                     131                                                                              CH.sub.2CH.sub.2CCH                                                                       CH.sub.3                                                                              OCH.sub.3     O  CH                                    132                                                                              CH.sub.2CH.sub.2CCH                                                                       OCH.sub.3                                                                             OCH.sub.3     O  CH                                    133                                                                              CH.sub.2CH.sub.2C CH                                                                      CH.sub.3                                                                              CH.sub.3      O  CH                                    134                                                                              CH.sub.2CH.sub.2CCH                                                                       CH.sub.2OCH.sub.3                                                                     OCH.sub.3     O  CH                                    135                                                                              CH.sub.2CH.sub.2CCH                                                                       CH.sub.3                                                                              Cl            O  CH                                    136                                                                              CH.sub.2CH.sub.2CCH                                                                       OCH.sub.3                                                                             Cl            O  CH                                    137                                                                              CH.sub.2CH.sub.2CCH                                                                       OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                            O  CH                                    138                                                                              CH.sub.2 CCH                                                                              CH.sub.3                                                                              OCF.sub.2CHFCl                                                                              O  CH m.p. 153-155°               139                                                                              CH.sub.2CCH CH.sub.3                                                                              OCF.sub.2CHF.sub.2                                                                          O  CH m.p. 171-173°               __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR12##                                                                                                              Physical                            No.                                                                              A           R.sub.1                                                                              R.sub.3                                                                            R.sub.4   X E  data                                __________________________________________________________________________    201                                                                              CH.sub.2CCH 6-Cl   CH.sub.3                                                                           OCH.sub.3 O N                                      202                                                                              CH.sub.2CCH 6-Cl   CH.sub.3                                                                           OCH.sub.3 O CH                                     203                                                                              CH.sub.2CCH 6-Cl   C.sub.2 H.sub.5                                                                    OCH.sub.3 O N                                      204                                                                              CH.sub.2CCH 6-Cl   OCH.sub.3                                                                          OCH.sub.3 O CH                                     205                                                                              CH.sub.2CCH 6-Cl   OCH.sub.3                                                                          OCH.sub.3 O N                                      206                                                                              CH.sub.2CCCH.sub.3                                                                        6-Cl   OCH.sub.3                                                                          CH.sub.3  O N                                      207                                                                              CH.sub.2CCCH.sub.3                                                                        6-Cl   OCH.sub.3                                                                          CH.sub.3  O CN                                     208                                                                              CH.sub.2CH.sub.2CCH                                                                       6-Cl   OCH.sub.3                                                                          CH.sub.3  O N                                      209                                                                              CH.sub.2CCH 6-OCH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3 O CH                                     210                                                                              CH.sub.2CCH 6-OCH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3 O N                                      211                                                                              CH.sub.2CCH 6-OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                    OCH.sub.3 O N                                      212                                                                              CH.sub.2CCH 6-OCH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3 O N                                      213                                                                              CH.sub.2C CH                                                                              6-OCH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3 O CH                                     214                                                                              CH.sub.2CCH 6-CH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3 O N                                      215                                                                              CH.sub.2CCH 6-CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  O CH                                     216                                                                              CH.sub.2CCH 6-CH.sub.3                                                                           OCH.sub.3                                                                          OCH.sub.3 O CH                                     217                                                                              CH.sub.2CCH 6-CH.sub.3                                                                           OCH.sub.3                                                                          OCH.sub.3 O N                                      218                                                                              CH.sub.2CCH 6-NO.sub.2                                                                           CH.sub.3                                                                           OCH.sub.3 O N                                      219                                                                              CH.sub.2CCH 6-NO.sub.2                                                                           CH.sub.3                                                                           OCH.sub.3 O CH                                     220                                                                              CH.sub.2CCH 6-NO.sub.2                                                                           OCH.sub.3                                                                          OCH.sub.3 O CH                                     221                                                                              CH.sub.2CCH 6-NO.sub.2                                                                           OCH.sub.3                                                                          OCH.sub.3 O N                                      222                                                                              CH.sub.2CCH 6-COOCH.sub.3                                                                        OCH.sub.3                                                                          CH.sub.3  O CH                                     223                                                                              CH.sub.2CCH 6-COOCH.sub.3                                                                        CH.sub.3                                                                           CH.sub.3  O N                                      224                                                                              CH.sub.2CCH 6-COOCH.sub.3                                                                        OCH.sub.3                                                                          OCH.sub.3 O N                                      225                                                                              CH.sub.2CCH 6-COOCH.sub.3                                                                        OCH.sub.3                                                                          OCH.sub.3 O CH                                     226                                                                              CH.sub.2CCH 5-Cl   CH.sub.3                                                                           OCH.sub.3 O N  m.p. 177°                    227                                                                              CH.sub.2CCH 5-Cl   CH.sub.3                                                                           OCH.sub.3 O CH m.p. 208°                    228                                                                              CH.sub.2CCH 5-Cl   OCH.sub.3                                                                          OCH.sub.3 O N                                      229                                                                              CH.sub.2CCH 5-Cl   OCH.sub.3                                                                          OCH.sub.3 O N                                      230                                                                              CH.sub.2C CH                                                                              5-Cl   C.sub.2 H.sub.5                                                                    CH.sub.3  O N                                      231                                                                              CH.sub.2CH.sub.2CCH                                                                       5-Cl   CH.sub.3                                                                           OCH.sub.3 O N                                      232                                                                              CH.sub.2CH.sub.2CCH                                                                       5-Cl   CH.sub.3                                                                           OCH.sub.3 O CH                                     233                                                                              CH.sub.2CCCH.sub.3                                                                        5-Cl   CH.sub.3                                                                           OCH.sub.3 O CH                                     234                                                                              CH.sub.2CCCH.sub.3                                                                        5-Cl   CH.sub.3                                                                           OCH.sub.3 O N                                      235                                                                              CH.sub.2CCCH.sub.3                                                                        5-Cl   C.sub.2 H.sub.5                                                                    OCH.sub.3 O N                                      236                                                                              CH.sub.2CCCH.sub.3                                                                        5-Cl   OCH.sub.3                                                                          OCH.sub.3 O N                                      237                                                                              CH.sub.2CCCH.sub.3                                                                        5-Cl   OCH.sub.3                                                                          OCH.sub.3 O CH                                     238                                                                              CH.sub.2CCH 5-F    CH.sub.3                                                                           OCH.sub. 3                                                                              O N  m.p. 158°                    239                                                                              CH.sub.2CCH 5-F    CH.sub.3                                                                           OCH.sub.3 O CH m.p. 211°                                                              (decomp.)                           240                                                                              CH.sub.2CCH 5-F    OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                         O N                                      241                                                                              CH.sub.2CCH 5-F    OCH.sub.3                                                                          OCH.sub.3 O CH                                     242                                                                              CH.sub.2CCH 5-NO.sub.2                                                                           OCH.sub.3                                                                          OCH.sub.3 O N                                      243                                                                              CH.sub.2CCH 5-NO.sub.2                                                                           CH.sub.3                                                                           CH.sub.3  O N                                      244                                                                              CH.sub.2CCH 5-NO.sub.2                                                                           CH.sub.3                                                                           OCH.sub.3 O CH                                     245                                                                              CH.sub.2CCH 5-CH(CH.sub.3).sub.2                                                                 CH.sub.3                                                                           OCH.sub.3 O N                                      246                                                                              CH.sub.2CCH 5-CH(CH.sub.3).sub.2                                                                 CH.sub.3                                                                           OCH.sub.3 O CH                                     247                                                                              CH.sub.2CCH 5-CH(CH.sub.3).sub.2                                                                 C.sub.2 H.sub.5                                                                    OCH.sub.3 O N                                      248                                                                              CH.sub.2CCH 5-CH(CH.sub.3).sub.2                                                                 OCH.sub.3                                                                          OCH.sub.3 O N                                      249                                                                              CH.sub.2CH.sub.2CCH                                                                       5-CH(CH.sub.3).sub.2                                                                 OCH.sub.3                                                                          OCH.sub.3 O N                                      250                                                                              CH.sub.2CH.sub.2CCH                                                                       5-CH(CH.sub.3).sub.2                                                                 OCH.sub.3                                                                          CH.sub.3  O N                                      251                                                                              CH.sub.2CH.sub.2CCH                                                                       5-CH(CH.sub.3).sub.2                                                                 OCH.sub.3                                                                          OCH.sub.3 O CH                                     252                                                                              CH.sub.2CCCH.sub.3                                                                        5-CH(CH.sub.3).sub.2                                                                 OCH.sub.3                                                                          OCH.sub.3 O N                                      253                                                                              CH.sub.2CCCH.sub.3                                                                        5-CH(CH.sub.3).sub.2                                                                 OCH.sub.3                                                                          OCH.sub.3 O CH                                     254                                                                              CH.sub.2C CCH.sub.3                                                                       5-CH(CH.sub.3).sub.2                                                                 OCH.sub.3                                                                          CH.sub.3  O N                                      255                                                                              CH.sub.2CCCH.sub.3                                                                        5-CH(CH.sub.3).sub.2                                                                 OCH.sub.3                                                                          CH.sub.3  O CH                                     256                                                                              CH.sub.2CCH 5-CH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3 O N                                      257                                                                              CH.sub.2CCH 5-CH.sub.3                                                                           CH.sub.3                                                                           OCHF.sub.2                                                                              O CH m.p. 201-203°                258                                                                              CH.sub.2CCH 5-CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    OCH.sub.3 O N                                      259                                                                              CH.sub.2CCH 5-CH.sub.3                                                                           OCH.sub.3                                                                          OCH.sub.3 O N                                      260                                                                              CH.sub.2CCH 5-CH.sub.3                                                                           OCH.sub.3                                                                          OCH.sub.3 O CH                                     261                                                                              CH.sub.2CCH 5-OCH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3 O CH                                     262                                                                              CH.sub.2C CH                                                                              5-OCH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3 O CH                                     263                                                                              CH.sub.2CCH 5-OCH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3 O N                                      264                                                                              CH.sub.2CCH 5-OCH.sub.3                                                                          OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                         O N                                      265                                                                              CH.sub.2CCH 5-COOCH.sub.3                                                                        CH.sub.3                                                                           OCH.sub.3 O N                                      266                                                                              CH.sub.2CCH 5-COOCH.sub.3                                                                        CH.sub.3                                                                           OCH.sub.3 O CH                                     267                                                                              CH.sub.2CCH 5-COOCH.sub.3                                                                        OCH.sub.3                                                                          OCH.sub.3 O N                                      268                                                                              CH.sub.2CCH 5-COOCH.sub.3                                                                        OCH.sub.3                                                                          OCH.sub.3 O CH                                     269                                                                              CH.sub.2CCH 3-NO.sub.2                                                                           CH.sub.3                                                                           OCH.sub.3 O CH                                     270                                                                              CH.sub.2CCH 3-NO.sub.2                                                                           CH.sub.3                                                                           OCH.sub.3 O N                                      271                                                                               CH.sub.2CCH                                                                              3-NO.sub.2                                                                           C.sub.2 H.sub.5                                                                    OCH.sub.3 O N                                      272                                                                              CH.sub.2CCH 3-NO.sub.2                                                                           OCH.sub.3                                                                          OCH.sub.3 O N                                      273                                                                              CH.sub.2CCH 3-OCH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3 O N                                      274                                                                              CH.sub.2CCH 3-OCH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3 O CH                                     275                                                                              CH.sub.2CCH 3-OCH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3 O CH                                     276                                                                              CH.sub.2CCH 3-OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                    OCH.sub.3 O N                                      277                                                                              CH.sub.2CCH 3-OCH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3 O N                                      278                                                                              CH.sub.2CCH 3-CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3  O CH                                     279                                                                              CH.sub.2C CH                                                                              3-CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    CH.sub.3  O N                                      280                                                                              CH.sub.2CCH 3-CH.sub.3                                                                           OCH.sub.3                                                                          CH.sub.3  O N                                      281                                                                              CH.sub.2CCH 3-Cl   OCH.sub.3                                                                          CH.sub.3  O CH                                     282                                                                              CH.sub.2CCH 3-Cl   OCH.sub.3                                                                          CH.sub.3  O CH                                     283                                                                              CH.sub.2CCH 3-Cl   OCH.sub.3                                                                          CH.sub.3  O N                                      284                                                                              CH.sub.2CCH 3-Cl   OCH.sub.3                                                                          OCH.sub.3 O N                                      285                                                                              CH.sub.2CCH 3-Cl   OCH.sub.3                                                                          OCH.sub.3 O CH                                     286                                                                              CH.sub.2CCH 5-Br   OCH.sub.3                                                                          CH.sub.3  O N  m.p. 187-188°                287                                                                              CH.sub.2CCH 5-CH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3 O N                                      288                                                                              CH.sub.2C CH                                                                              5-CH.sub.3                                                                           OCH.sub.3                                                                          Cl        O CH m.p. 202-204°                289                                                                              CH.sub.2CCH 5-F    OCH.sub.3                                                                          OCH.sub.3 O N  m.p. 182-183°                290                                                                              CH.sub.2CCH 5-Cl   OCHF.sub.2                                                                         CH.sub.2  O CH m.p. 175-176°                                                          (decomp.)                           291                                                                              CH.sub.2CCH 5-F    OCHF.sub.2                                                                         CH.sub.3  O CH m.p. 175°                                                              (decomp.)                           292                                                                              CH.sub.2CCH H      OCHF.sub.2                                                                         OCH.sub.3 O CH                                     293                                                                              CH.sub.2CCH H      OCHF.sub.2                                                                         Cl        O CH                                     294                                                                              CH.sub.2CCH H      CH.sub.3                                                                           OCF.sub.2CHF.sub.2                                                                      O CH                                     295                                                                              CH.sub.2CCH H      OCH.sub.3                                                                          OCF.sub.2 CHF.sub.2                                                                     O CH                                     296                                                                              CH.sub.2CCH H      Cl   OCF.sub.2CHF.sub.2                                                                      O CH                                     297                                                                              CH.sub.2CCH H      CH.sub.3                                                                           OCF.sub.2CHFCl                                                                          O CH                                     298                                                                              CH.sub.2CCH H      OCH.sub.3                                                                          OCF.sub.2CHFCl                                                                          O CH                                     299                                                                              CH.sub.2CCH H      Cl   OCF.sub.2CHFCl                                                                          O CH                                     300                                                                              CH.sub.2CCH 5-Cl   CH.sub.3                                                                           CH.sub.3  O CH m.p. 206-208°                                                          (decomp.)                           301                                                                              CH.sub.2CCH 5-F    CH.sub.3                                                                           CH.sub.3  O CH m.p. 219-220°                                                          (decomp.)                           __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR13##                                                                                   Position                                                       No.                                                                              A           of XA                                                                              R.sub.1                                                                             R.sub.2                                                                            X E  Physical data                             __________________________________________________________________________    401                                                                              CH.sub.2CCH 5    2-CH.sub.3                                                                          H    O N                                            402                                                                              CH.sub.2CCCH.sub.3                                                                        5    2-CH.sub.3                                                                          H    O CH                                           403                                                                              CH.sub.2CH.sub.2CCH                                                                       5    2-CH.sub.3                                                                          H    O CH                                           404                                                                              CH.sub.2CH.sub.2C CH                                                                      5    2-CH.sub.3                                                                          H    O N                                            405                                                                              CH.sub.2CCCH.sub.3                                                                        5    2-CH.sub.3                                                                          H    O N                                            406                                                                              CH.sub.2CCH 5    2-CH.sub.3                                                                          H    O CH                                           407                                                                              CH.sub. 2CCH                                                                              5    2-Cl  H    O N  m.p. 175°-176°              408                                                                              CH.sub.2CCH 5    2-Cl  H    O CH                                           409                                                                              CH.sub.2CCCH.sub.3                                                                        5    2-Cl  H    O CH                                           410                                                                              CH.sub.2CCCH.sub.3                                                                        5    2-Cl  H    O N                                            411                                                                              CH.sub.2CH.sub.2CCH                                                                       5    2-Cl  H    O N                                            412                                                                              CH.sub.2CH.sub.2CCH                                                                       5    2-Cl  H    O CH                                           413                                                                              CH.sub.2CH.sub. 2CCH                                                                      5    2-CH.sub.3                                                                          H    O N                                            414                                                                              CH.sub.2CCH 3    2-CH.sub.3                                                                          H    O CH                                           415                                                                              CH.sub.2CCCH.sub.3                                                                        3    2-CH.sub.3                                                                          H    O CH                                           416                                                                              CH.sub.2CCH 3    2-CH.sub.3                                                                          H    O N                                            417                                                                              CH.sub.2CCH 3    2-OCH.sub.3                                                                         H    O CH                                           418                                                                              CH.sub.2CCH 3    2-OCH.sub.3                                                                         H    O N                                            419                                                                              CH.sub.2CCCH.sub.3                                                                        3    2-OCH.sub.3                                                                         H    O N                                            420                                                                              CH.sub.2CCCH.sub.3                                                                        3    2-OCH.sub.3                                                                         H    O CH                                           421                                                                              CH.sub.2CH.sub.2CCH                                                                       3    2-OCH.sub.3                                                                         H    O CH                                           422                                                                              CH.sub.2CH.sub.2 CCH                                                                      3    2-OCH.sub.3                                                                         H    O N                                            423                                                                              CH.sub.2CCH 5    2-OCH.sub.3                                                                         H    O N                                            424                                                                              CH.sub.2CCH 5    2-OCH.sub.3                                                                         H    O CH                                           425                                                                              CH.sub.2CCCH.sub.3                                                                        5    2-OCH.sub.3                                                                         H    O CH                                           426                                                                              CH.sub.2CCCH.sub.3                                                                        5    2-OCH.sub.3                                                                         H    O N                                            427                                                                              CH.sub.2CH.sub.2CCH                                                                       5    2-OCH.sub.3                                                                         H    O N                                            428                                                                              CH.sub.2CH.sub.2CCH                                                                       5    2-OCH.sub.3                                                                         H    O CH                                           429                                                                              CH.sub.2CCH 3    5-Br  2-OCH.sub.3                                                                        O N                                            430                                                                              CH.sub.2CCH 3    5-Br  2-OCH.sub.3                                                                        O CH                                           431                                                                              CH.sub.2C CCH.sub.3                                                                       3    5-Br  2-OCH.sub.3                                                                        O CH                                           432                                                                              CH.sub.2CCCH.sub.3                                                                        3    5-Br  2-OCH.sub.2                                                                        O N                                            433                                                                              CH.sub.2CCH 3    5-COOCH.sub.3                                                                       2-OCH.sub.3                                                                        O N                                            434                                                                              CH.sub.2CCH 3    5-COOCH.sub.3                                                                       2-OCH.sub.3                                                                        O CH                                           435                                                                              CH.sub.2CH.sub.2CCH                                                                       3    5-COOCH.sub.3                                                                       2-OCH.sub.3                                                                        O CH                                           436                                                                              CH.sub.2CH.sub.2CCH                                                                       3    5-COOCH.sub.3                                                                       2-OCH.sub.3                                                                        O N                                            437                                                                              CH.sub.2CCH 3    5-COOCH.sub.3                                                                       2-OCH.sub.3                                                                        O N                                            438                                                                              CH.sub.2CCH 3    5-COOCH.sub.3                                                                       2-OCH.sub.3                                                                        O CH                                           439                                                                              CH.sub.2CCH 2    5-NO.sub.2                                                                          3-CF.sub.3                                                                         O N                                            440                                                                              CH.sub. 2CCH                                                                              2    5-NO.sub.2                                                                          3-CF.sub.3                                                                         O CH                                           441                                                                              CH.sub.2CCH 2    5-NO.sub.2                                                                          3-Cl O CH                                           442                                                                              CH.sub.2CCH 2    5-NO.sub.2                                                                          3-Cl O N                                            443                                                                              CH.sub.2CCCH.sub.3                                                                        2    5-NO.sub.2                                                                          3-Cl O N                                            444                                                                              CH.sub.2CCCH.sub.3                                                                        2    5-NO.sub.2                                                                          3-Cl O CH                                           445                                                                              CH.sub.2CCH 2    5-CF.sub.3                                                                          3-NO.sub.2                                                                         O CH                                           446                                                                              CH.sub.2CCH 2    5-CF.sub.3                                                                          3-NO.sub.2                                                                         O N                                            447                                                                              CH.sub.2CCH 2    5-CH.sub.3                                                                          3-CH.sub.3                                                                         O N                                            448                                                                              CH.sub.2CCH 2    5-CH.sub.3                                                                          3-CH.sub.3                                                                         O CH                                           449                                                                              CH.sub.2CH.sub. 2CCH                                                                      2    5-CH.sub.3                                                                          3-CH.sub.3                                                                         O CH                                           450                                                                              CH.sub.2CH.sub.2CCH                                                                       2    5-CH.sub.3                                                                          3-CH.sub.3                                                                         O N                                            451                                                                              CH.sub.2CCH 2    5-Cl  3-NO.sub.2                                                                         O N                                            452                                                                              CH.sub.2CCH 2    5-Cl  3-NO.sub.2                                                                         O CH                                           453                                                                              CH.sub.2CCCH.sub.3                                                                        2    5-Cl  3-NO.sub.2                                                                         O CH                                           454                                                                              CH.sub.2CCCH.sub.3                                                                        2    5-Cl  3-NO.sub.2                                                                         O N                                            455                                                                              CH.sub.2CCH 2    5-Cl  3-Cl O N                                            456                                                                              CH.sub.2CCH 2    5-Cl  3-Cl O CH                                           457                                                                              CH.sub.2CCCH.sub.3                                                                        2    5-Cl  3-Cl O CH                                           458                                                                              CH.sub.2C CCH.sub.3                                                                       2    5-Cl  3-Cl O N                                            459                                                                              CH.sub.2CH.sub.2CCH                                                                       2    5-Cl  3-Cl O N                                            460                                                                              CH.sub.2CH.sub.2CCH                                                                       2    5-Cl  3-Cl O CH                                           461                                                                              CH.sub.2CH.sub.2CCH                                                                       2    5-Br  3-OCH.sub.3                                                                        O N                                            462                                                                              CH.sub.2CH.sub.2CCH                                                                       2    5-Br  3-OCH.sub.3                                                                        O CH                                           463                                                                              CH.sub.2CCH 3    5-Br  2-OCH.sub.3                                                                        O CH                                           464                                                                              CH.sub.2CCH 3    5-Br  2-OCH.sub.3                                                                        O N                                            465                                                                              CH.sub.2CCH 2    5-COOCH.sub.3                                                                       3-OCH.sub.3                                                                        O N                                            466                                                                              CH.sub.2CCH 2    5-COOCH.sub.3                                                                       3-OCH.sub.3                                                                        O CH                                           467                                                                              CH.sub.2C CCH.sub.3                                                                       3    5-COOCH.sub.3                                                                       2-OCH.sub.3                                                                        O CH                                           468                                                                              CH.sub.2CCCH.sub.3                                                                        3    5-COOCH.sub.3                                                                       2-OCH.sub.3                                                                        O N                                            469                                                                              CH.sub.2CH.sub.2CCH                                                                       3    5-COOCH.sub.3                                                                       3-OCH.sub.3                                                                        O N                                            470                                                                              CH.sub.2CH.sub.2CCH                                                                       3    5-COOCH.sub.3                                                                       3-OCH.sub.3                                                                        O CH                                           471                                                                              CH.sub.2CH.sub.2CCH                                                                       3    5-CH.sub.3                                                                          3-Br O CH                                           472                                                                              CH.sub.2CH.sub.2CCH                                                                       2    5-CH.sub.3                                                                          3-Br O N                                            473                                                                              CH.sub.2CCH 2    5-CH.sub.3                                                                          3-Br O N                                            474                                                                              CH.sub.2CCH 2    5-CH.sub.3                                                                          3-Br O CH                                           475                                                                              CH.sub.2CCH 2    5-Br  3-NO.sub.2                                                                         O N                                            476                                                                              CH.sub.2C CH                                                                              2    5-Br  3-NO.sub.2                                                                         O CH                                           477                                                                              CH.sub.2CCH 2    5-Cl  3-Br O N                                            478                                                                              CH.sub.2CCCH.sub.3                                                                        2    5-Cl  3-Br O N                                            479                                                                              CH.sub.2CCCH.sub.3                                                                        2    5-Cl  3-Br O CH                                           480                                                                              CH.sub.2CCH 2    5-Cl  3-Br O CH                                           481                                                                              CH.sub.2CH.sub.2CCH                                                                       2    5-Cl  3-Br O N                                            482                                                                              CH.sub.2CCH 5    2-NO.sub.2                                                                          H    O CH                                           483                                                                              CH.sub.2CCH 5    2-NO.sub.2                                                                          H    O N                                            484                                                                              CH.sub.2CCH 5    2-Cl  H    O N                                            485                                                                              CH.sub.2CCH 5    2-Cl  H    O CH                                           486                                                                              CH.sub.2CCCH.sub.3                                                                        5    2-Cl  H    O CH                                           487                                                                              CH.sub.2CCCH.sub.3                                                                        5    2-Cl  H    O N                                            488                                                                              CH.sub.2CH.sub.2CCH                                                                       5    2-Cl  H    O N                                            489                                                                              CH.sub.2CH.sub.2CCH                                                                       5    2-Cl  H    O CH                                           __________________________________________________________________________

FORMULATION EXAMPLES EXAMPLE 3 Formulation Examples for activeingredients of the formula I (%=percent by weight)

    ______________________________________                                        (a) Wettable powder                                                                              (a)      (b)      (c)                                      ______________________________________                                        active ingredient  20%      60%      0.5%                                     sodium lignin sulfonate                                                                          5%       5%       5%                                       sodium lauryl sulfate                                                                            3%       --       --                                       sodium diisobutylnaphthalene                                                                     --       6%       6%                                       sulfonate                                                                     octylphenolpolyethylene glycol                                                                   --       2%       2%                                       ether (7-8 mols of ethylene oxide)                                            highly dispersed silicic acid                                                                    5%       27%      27%                                      kaolin             67%      --       --                                       sodium chloride    --       --       59.5%                                    ______________________________________                                    

The active ingredients is well mixed with the additives and ground in asuitable mill. There are obtained wettable powders which can be dilutedwith water to give suspensions of the concentration desired.

    ______________________________________                                        (b) Emulsion concentrate                                                                             (a)    (b)                                             ______________________________________                                        active ingredient      10%    1%                                              octylphenolpolyethylene glycol ether                                                                  3%    3%                                              (4-5 mols of ethylene oxide)                                                  calcium dodecyl benzene sulfonate                                                                     3%    3%                                              castor oil polyglycol ether                                                                           4%    4%                                              (36 mols of ethylene oxide)                                                   cyclohexanone          30%    10%                                             xylene mixture         50%    79%                                             ______________________________________                                    

Emulsions of the concentration desired can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        (c) Dust          (a)     (b)                                                 ______________________________________                                        active ingredient  0.1%    1%                                                 talcum            99.9%   --                                                  kaolin            --      99%                                                 ______________________________________                                    

Dusts ready for use are obtained by mixing the active-ingredient withthe carriers, and grinding the mixture in a suitable mill.

    ______________________________________                                        (d) Extruder granulate                                                                            (a)    (b)                                                ______________________________________                                        active ingredient   10%    1%                                                 sodium lignin sulfonate                                                                            2%    2%                                                 carboxymethylcellulose                                                                             1%    1%                                                 kaolin              87%    96%                                                ______________________________________                                    

The active ingredient is mixed with the additives, and the mixture isthen ground and moistened with water. It is extruded and subsequentlydried in a stream of air.

    ______________________________________                                        (3) Coated granulate                                                          ______________________________________                                        active ingredient    3%                                                       polyethylene glycol (MG 200)                                                                       3%                                                       kaolin               94%                                                      ______________________________________                                    

The finely ground active ingredient is uniformuly applied, in a mixer,to the kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        (f) Suspension concentrate                                                                           (a)    (b)                                             ______________________________________                                        active ingredient      40%    5%                                              ethylene glycol        10%    10%                                             nonylphenolpolyethylene glycol                                                                        6%    1%                                              ether (15 mols of ethylene oxide)                                             sodium lignin sulfonate                                                                              10%    5%                                              carboxymethylcellulose  1%    1%                                              37% aqueous formaldehyde solution                                                                    0.2%   0.2%                                            silicone oil in the form of a                                                                        0.8%   0.8%                                            75% aqueous emulsion                                                          water                  32%    77%                                             ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadditives. There is thus obtained a suspension concentrate from whichcan be produced, by dilution with water, suspensions of theconcentration desired.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        active ingredient      5%                                                     isopropylamine         1%                                                     octylphenolpolyethylene glycol ether                                                                 3%                                                     (78 mols of ethylene oxide)                                                   water                  91%.                                                   ______________________________________                                    

BIOLOGICAL EXAMPLES EXAMPLE 4 Verification of the herbicidal activitybefore emergence of the plants

Plant seeds are sown in flower pots (12-15 cm diameter) in a greenhouse.The surface of the soil is treated immediately afterwards with anaqueous dispersion or solution of the active ingredients, theconcentration used being 4 kg of active ingredient per hectare. The potsare then kept in the greenhouse at a temperature of 22°-25° C. with50-70% relative humidity. The test results are evaluated after 3 weeks,and the action on the test plants is assessed according to the followingscale of ratings:

    ______________________________________                                        1       plants have not emerged or are totally destroyed                      2-3     very strong action                                                    4-6     medium action                                                         7-8     weak action                                                           9       no action (as untreated control plants).                              ______________________________________                                    

    ______________________________________                                        Pre-emergence action                                                          Applied amount: 4 kg of active ingredient/hectare                             Comp. No.  Avena   Setaria   Sinapis                                                                             Stellaria                                  ______________________________________                                         8         6       6         2     2                                          19         2       2         2     2                                          21         3       3         2     2                                          23         2       2         2     2                                          29         6       4         3     4                                          38         3       3         2     2                                          48         6       5         2     2                                          68         5       5         2     2                                          84         4       4         2     2                                          87         4       2         2     2                                          93         2       1         2     1                                          94         2       3         2     2                                          226        5       5         2     2                                          227        5       6         2     2                                          238*       4       5         2     2                                          239*       3       4         2     2                                          286        7       8         2     2                                          289*       6       6         2     2                                          407        6       6         3     3                                          ______________________________________                                         *Applied amount: 0.5 kg of active ingredient/hectare                     

EXAMPLE 5 Verification of selectivity on pre-emergence application

With the same test procedure as in Example 4, a number of varieties ofplant seeds are treated with various applied amounts of activeingredient. The test results are evaluated according to the same scaleof ratings.

    ______________________________________                                        Pre-emergence action:                                                         Action                                                                        applied amount in                                                             kg of AS*/hectare                                                                            Comp. No. 23 Comp. No. 93                                      test plant     0.125   0.06     0.125 0.06                                    ______________________________________                                                       9       9        8     9                                       Alopecurus myos                                                                              2       3        2     2                                       Echinochloa c.g.                                                                             3       3        2     2                                       Rottboellia ex.                                                                              8       9        4     4                                       Abutilon       2       2        2     2                                       Xanthium Sp.   2       3        6     6                                       Chenopodium Sp.                                                                              3       3        2     2                                       Ipomoea        1       2        3     2                                       Sinapis        2       2        2     2                                       Galium aparine 2       2        1     1                                       Viola tricolor 3       4        2     2                                       ______________________________________                                         *active substance                                                        

EXAMPLE 6 Demonstration of the herbicidal activity after emergence ofthe plants (contact action)

A number of weeds and cultivated plants, both monocotyledons anddicotyledons, are sprayed in the 4- to 6- leaf stage with an aqueousactive-ingredient dispersion in dosages of 4 kg of active substance perhectare, and then kept at 24° to 26° C. with 45-60% relative humidity.The test results are evaluated 15 days after the treatment, and anassessment made according to the same scale of ratings as in thepre-emergence test.

    ______________________________________                                        Post-emergence action                                                         Applied amount: 4 kg of active ingredient per hectare                         Comp.                       Sola-      Stel- Phase-                           No.   Avena   Setaria Lolium                                                                              num  Sinapis                                                                             laria olus                             ______________________________________                                         8    8       8       3     3    2     3     3                                19    2       4       3     2    2     3     3                                21    5       4       4     2    2     2     4                                23    2       3       2     2    2     2     2                                38    4       5       2     2    2     2     3                                48    6       5       4     2    2     2     4                                68    6       6       2     3    2     2     3                                84    6       5       2     2    2     2     3                                87    5       5       2     3    2     3     4                                93    4       2       4     2    2     3     3                                94    4       3       2     2    2     2     4                                226   7       7       3     3    3     3     4                                227   7       8       4     3    3     4     4                                238*  7       6       3     2    2     2     3                                239*  4       4       2     3    2     3     3                                289*  9       9       3     4    2     2     4                                ______________________________________                                         *Applied amount: 0.5 kg of active ingredient per hectare                 

EXAMPLE 7 Verification of selectivity with post-emergence application

With the same test procedure as in Example 6, a largish number of plantsare treated with various applied amounts of active ingredient. The testresults are evaluated according to the scale of ratings given in Example4.

    ______________________________________                                        Post-emergence action                                                         Action                                                                        applied amount in                                                                         Comp.      Comp.      Comp.                                       kg of AS/hectare                                                                           No. 23     No. 38     No. 93                                     test plants 0.125   0.06   0.125 0.06 0.125 0.06                              ______________________________________                                        wheat       9       9      9     9    8     9                                 maize       3       3      4     5    9     9                                 rice (dry)  4       6      6     7    9     9                                 Alopecurus myos.                                                                          3       3      4     4    1     2                                 Cyperus escul.                                                                            9       9      3     3    4     9                                 soya-bean   2       2      6     6    9     9                                 cotton      4       4      7     7    9     9                                 Sinapis     2       3      2     2    1     1                                 Galium aparine                                                                            4       4      4     4    1     1                                 Viola tricolor                                                                            3       3      4     4    2     2                                 ______________________________________                                    

EXAMPLE 8 Verification of sprouting inhibition on stored potatoes

A number of commercially available potatoes of the "Urgenta" variety,exhibiting no germination (sprouting), are washed and dried. Thepotatoes are afterwards each immersed for one minute inactive-ingredient emulsions of varying concentration; they are then laidout on filter paper in plastic dishes, and stored at temperatures of 14°and 21° C. in darkness with 50% relative humidity, and an evaluation ismade 34 days after application. At the same time the loss in weight ofthe tubers and the weight of the sprouts, compared with those values inthe case of the untreated control specimens are determined. Thecompounds according to the invention brought about in this test acomplete prevention of sprouting. The loss in weight of the potatoes wasless than 10% of that of the control potatoes.

EXAMPLE 9 Verification of the reduction in growth of tropical leguminouscover crops

The test plants (centrosema plumieri and centrosema pubescens) arecultivated up to the fully grown stage, and then cut back to a height of60 cm. After 7 days, the active substance is sprayed on in the form ofan aqueous emulsion. The test plants are maintained at 70% relativehumidity and with 6000 lux of artificial light, 14 hours per day, attemperatures of 27° by day and 21° C. by night. The test results areassessed 4 weeks after application of the emulsion. The new growthoccurring compared with that on the control plants is estimated andweighed, and the phytotoxicity is evaluated. The plants treated with theactive ingredients of the formula I show in this test a clear reductionin new growth (less than 20% of the new growth occurring on untreatedcontrol plants), without the test plants having suffered damage.

EXAMPLE 10 Regulation of growth of soya-beans

Soya-beans of the variety "Hark" are sown in plastic containers holdinga soil/peat/sand mixture in the ratio of 6:3:1, and are placed into aclimatic chamber. By optimum choice of temperature, illumination,fertiliser addition and watering, the plants develop over about 5 weeksinto the 5-6 trifoliate stage. At this point, the plants are sprayeduntil thoroughly dripping wet with the aqueous liquor of an activeingredient of the formula I, the active-ingredient concentration beingup to 100 g of AS/hectare. An assessment of the results is made about 5weeks after application of the active ingredient. The active ingredientsof the formula I produce a marked increase in the number and in theweight of the pods on the leading shoots compared with the number andweight of pods on the untreated control plants.

What is claimed is:
 1. An N-phenylsulfonyl-N'-pyrimidinyl- or-triazinyl-urea of the general formula I ##STR14## wherein A is a C₃ -C₆-alkynyl group,X is oxygen, sulfur or a sulfinyl or sulfonyl bridge, Zis oxygen or sulfur, m is the number one or two, R₁ is hydrogen,halogen, C₁ -C₅ -alkyl or C₂ -C₅ -alkenyl or a group --Y--R₅, R₂ ishydrogen, halogen, C₁ -C₅ -alkyl, C₂ -C₅ -alkenyl or C₁ -C₄ -haloalkyl,or a group --Y--R₅, --COOR₆, --NO₂ or --CO--NR₇ --R₈, R₃ and R₄independently of one another are hydrogen, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkyl, C₁ -C₄ -haloalkoxy,halogen or alkoxyalkyl having at most 4 carbon atoms, R₅ and R₆ are eachC₁ -C₅ -alkyl, C₂ -C₅ -alkenyl or C₂ -C₆ -alkynyl, R₇ and R₈independently of one another are each hydrogen, C₁ -C₅ -alkyl, C₂ -C₅-alkenyl or C₂ -C₆ -alkynyl, and Y is oxygen, sulfur or a sulfinyl orsulfonyl bridge; and the salts of these compounds.
 2. A compoundaccording to claim 1, wherein Z is oxygen.
 3. A compound according toclaim 2, wherein one --X--A group is in the 2-position with respect tothe sulfonyl group, and R₃ and R₄ together contain no more than 4 carbonatoms.
 4. A compound according to claim 2, wherein one --X--A group isin each of the 2- and 5-positions with respect to the sulfonyl group,and R₃ and R₄ together contain no more than 4 carbon atoms.
 5. Acompound according to claim 3, wherein R₁ is hydrogen, and R₂ is in the5- or 6-position with respect to the sulfonyl group.
 6. A compoundaccording to claim 5, wherein R₂ is hydrogen, and R₃ and R₄ are each C₁-C₄ -alkyl, C₁ -C₄ -alkoxy, methylthio, 2,2,2-trifluoroethoxy,difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, halogen or alkoxyalkyl.
 7. Acompound according to claim 6, wherein X is oxygen.
 8. A compoundaccording to claim 7, wherein A is propargyl.
 9. A compound according toclaim 1, wherein Z is sulfur, X is oxygen or sulfur, R₃ and R₄independently of one another are each C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, C₁-C₃ -alkylthio, difluoromethoxy or 2,2,2-trifluoroethoxy with togetherat most 4 carbon atoms, and A is --CH₂ --C.tbd.CH, --CH₂ --C.tbd.C--CH₃,--CH₂ --CH₂ --C.tbd.CH, and the --X--A group occupies the 2-position,and m is the number
 1. 10.N-(2-propargylthiophenylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-ureaaccording to claim
 6. 11.N-(2-propargyloxyphenylsulfonyl)-N'-(4-methoxy-6-methylpyrimidin-2-yl)-ureaaccording to claim
 8. 12.N-(2-propargyloxyphenylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-ureaaccording to claim
 8. 13.N-(5-fluoro-2-propargyloxyphenylsulfonyl)-N'-(4-methoxy-6-methylpyrimidin-2-yl)-ureaaccording to claim
 5. 14. A herbicidal and plant-growth-reducingcomposition which contains, as active ingredient, at least oneN-phenylsulfonyl-N'-pyrimidinylurea of the formula I, claim 1, togetherwith carriers and/or other additives.
 15. A method of controllingundesired plant growth, which method comprises applying thereto or tothe locus thereof a herbicidally effective amount of a compoundaccording to claim
 1. 16. A method of suppressing plant growth, whichmethod comprises applying thereto or to the locus thereof an effectiveamount of a compound according to claim
 1. 17. A method of regulatingplant growth of cultivated plants in the meaning of increasing the yieldof the crops, which method comprises applying thereto or to the locusthereof an effective amount of a compound according to claim
 1. 18. Amethod according to claim 15 for selectively controlling weeds in cropsof cultivated plants, which method comprises applying the compound,preemergence or postemergence.
 19. A method according to claim 16 forsuppressing plant growth beyond the two-leaf stage, which methodcomprises applying the compound preemergence.
 20. A method according toclaim 18 in cereals.
 21. A method according to claim 17 in soybeans.